“I have walked across the surface of the Sun. I have witnessed events so tiny and so fast they can hardly be said to have occurred at all. But you, Adrian, you’re just a man. The world’s smartest man poses no more threat to me than does its smartest termite.” – Doctor Manhattan
The above quote by Doctor Manhattan from the 2009 movie, Watchmen, made a very big impact on me. Not only did Doctor Manhattan have extraordinary physical capabilities, but also boundless intelligence and wit. Most scintillating however, was his ability to observe and control miniscule atomic particles and impossibly fast to imagine metaphysical events. Doctor Manhattan didn’t really strike me as a lush, but I’m sure that he would have been fascinated with the chemically complex and ever changing matrix that is maturing wine.
As a former minor winemaker at quite a few cellars, my favorite place has always been the barrel maturation cellar. Barrel ageing is ostensibly one of a wine’s more important stages of evolution before bottling. But how exactly does wine change during barrel ageing and what effect does it have on the countless chemical reactions taking place in wine every second? The main effect of oak barrel ageing is twofold. Wood character is introduced (the rate and intensity is mostly dependent on fill status of the barrel) and oxygen is very slowly introduced to the wine. Generally speaking, this results in softening of the harsh tannins and flavors present at the end of fermentation. Oak is a fascinating substance, which has a profound and remarkable effect on the flavor chemistry of wine. Key oak derived compounds are tannin, lignin, cellulose and hemicellulose.
Tannin plays a vital role in barrel ageing. Although most tannin in wine comes from the grapes, some of it is also liberated by the barrel during ageing. So what exactly is the deal with tannin? An experienced winemaker will instinctively know how to optimally merge and balance the tannins extracted during the youthful stages (fermentation, skin contact and pressing) and the mature stages (barrel ageing and blending). For instance, more tannic grape varieties such as Tannat, Cabernet Sauvignon, Nebbiolo and Shiraz cannot be approached the same as the less tannic Pinot noir. Once again, winemaker experience is paramount.
OK, now hold on to your chemistry hat, here comes the hard (but interesting) bit! Phenolic compounds (consisting of natural phenols and polyphenols) in wine are largely responsible for imparting taste, colour and mouthfeel to wine. They include phenolic acid, stilbenes, flavonols, dihydroflavonols, anthocyanins, flavanol monomers (catechins) and flavanol polymers (proanthocyanidins). Natural phenols can be separated into flavonoids and non-flavonoids. The latter group includes stilbenoids such as resveratrol and phenolic acids such as benzoiz, caffeic and cinnamic acids. The former group includes anthocyanins and wait for it… tannins!
What would a good red wine be without vanilla flavors, sweet and toasty aromas and notes of tea and tobacco? Specific compounds create these nuances in finished wine, for example: volatile phenols containing vanillin; carbohydrate degradation products containing furfural, a component yielding a sweet and toasty aroma; “oak” lactones imparting a woody aroma; terpenes providing “tea” and “tobacco” notes, and hydrolysable tannins, which are important to the relative astringency of the wine. Take note, every time you’re quaffing a wine (hopefully a worthy vintage), you’re consuming everything you’ve just read above. If this doesn’t sit quite right with you, then I guess nothing much will.
They say you should have respect for your elders. So, tread lightly the next time you pass through a barrel maturation cellar. You might even see Doctor Manhattan skulking around in the dark, silent corners…
Bernard Mocke is a technical consultant for Oenobrands.
As discussed in previous postings, longevity may be considered within the pantheon of wine quality. The reductive strength of a wine is a measure of oxygen uptake and the ability to handle that uptake, that is improve with age. In red wines this is influenced principally by phenols and impacted by several winemaking protocols.
In a recent study (Kassas and Kennedy 2011) wines commanding the highest market value had several attributes in common including the highest concentrations of total tannins, the highest concentration of skin tannins and tannin-anthocyanin bound pigment polymers.
In grapes and wines, anthocyanin pigments can be either free monomers, that is, unbound, or associated with other compounds including phenols such as tannins to form polymers.
Tannin polymerization in fruit and wine continues until an anthocyanin molecule binds the terminal ends of the tannin chain forming ‘bookends’, thus stopping the polymerization. As such, the ratio of anthocyanins to tannins is important. This ratio impacts the extent of polymerization and, therefore, astringency.
Large tannin-tannin and tannin-anthocyanin polymers provide a relatively large number of binding sites to interact with proteins, as well as salivary proteins. As such, wines with an abundance of large polymers tend to lack softness and often possess a dry mouth sensation.
Conversely, smaller polymers have fewer protein binding sites and produce less astringency while providing a softer mouthfeel and often more palate depth. These smaller polymers are associated with enhanced reductive strength and wine aging potential.
Some phenols (diphenols) have the ability to react with oxygen, bind with another phenol, and recreate the original structure-thus allowing it to react over and over again. This helps explain the rather counter intuitive feature of exposing a young wine to oxygen and making that wine more resistant to oxidation. Young red wines can consume oxygen, actually increasing reductive strength.
Randall Grahm of Bonny Doon Vineyards in California considers reductive strength to be analogous to a wine’s chi or, as the Chinese say, life force. When a wine is young, it can share its chi with the world; when old, it must guard it so the wine does not diminish too quickly. Young wines have a capacity to adsorb oxygen and that can actually increase its resistance to later oxidation. Irrespective of chi, we believe that reductive strength is related to the phenolic composition of a wine and, therefore, to longevity.
“Experience is the name everyone give to the their mistakes” - Oscar Wilde
Dr Bruce Zoecklein is a Professor Emeritus, Enology-Grape Chemistry Group Virginia Tech.
His Enology Notes are available at www.vtwines.info.
The European Union might want to ban wine in which hen’s eggs or dairy products have been used, as some people can be allergic to these products. Alternatively the new law might just insist on labelling the wine as containing these products. The prevalence of allergic reactions to milk and egg products has been reported to be 1% of the adult population. Clinical trials have been inconclusive, and although wine has no history of causing allergic reactions as a result of the protein fining agents used, the possibility still exists.
Eggnog is a traditional drink at Christmas in the USA, and was developed in Europe by combining eggs and alcoholic drinks to let the eggs last longer. The drink was apparently first called “egg-and-grog”, and it has been known to cause allergic reactions in individuals. This seems to be the basis of the fear of egg allergens in wine.
Although HACCP is widely practised in the winemaking industry, almost all of the CCPs (critical control points) have a quality influence. There is only one commonly established real CCP and that is at bottling, to prevent glass from entering the bottles which could be harmful to people who swallow it. Another critical control point was once established to be grapes infected by Ochratoxin A, which is formed by moulds on grapes, but that is not very common.
The allergen law requires wine that contain these products to be labelled, but if there are no residues, who will be the wiser? The naughty compounds in eggs are the proteins that can easily be removed, although milk might leave residues of lactose. The ELISA tests that are used to test for residues cannot test down to zero, but the limits of detection have been found to be good enough to establish risk. There are also people with the view that if a product has been used, if it is still present or not, it must be stated.
There have been companies peddling plant alternative proteins that can apparently perform the same tasks as egg and milk proteins, but I have not had the pleasure to test these.
The new allergen labelling laws were originally intended to be implemented in 2005, but the deadline has now been extended to 30 June 2012, to assess possible exemption of these products. Let’s see what happens.
Délestage – (‘dehl-luh-STAJ’) aka “rack and return” (though the French sounds much more refined and romantic, as usual.) refers to the practice of repeatedly draining fermenting red wine off of its skins through a screen that traps some portion of the seeds, then returning the drained-off juice to continue fermenting on the skins, but minus the seeds entrapped in the draining process. Fewer seeds = lower seed-to-juice ratio = less extraction of seed tannins into juice = less tannic wine.
You know that it can’t really be that simple. There are two reasons why just describing the mechanics of the operation is inadequate. First, the “rack and return” process does more than just remove seeds. Like other methods of cap management*, the process also douses the floating grape skins. Unlike some other methods of cap management, délestage generally incorporates a lot of air into the must when the juice is pumped back over the skins.
Besides stimulating their growth, oxygen discourages fermentation yeasts from producing unsavory cooked cabbage and onion-like sulfides. Oxygen also has far-reaching and often poorly-understood effects on myriad elements of wine chemistry. Tannin polymerization, for example, is influenced by oxygen in complex ways that seem, in general, to lead to softer and rounder wines In fact, the role of oxygen in winemaking is so very complex that I’m going to refrain from saying any more about it here for fear of perjuring myself. In any case, the influence of délestage on a wine can’t just be attributed to removing seeds; oxygen must play a part, too.
The second reason why délestage is more complex than its mechanical description comes from our understanding – or, rather, our lack of understanding – of tannins themselves. We once separated tannins into the two broad categories of seed tannins and skin tannins. Seed tannins were bad: harsh, bitter, and green. Skin tannins were better: softer and malleable. In this context, délestage makes a lot of sense. Decreased exposure to bitter seeds during fermentation should reduce harsh, bitter flavors.
For better or for worse, tannin chemists, led by Dr. Jim Harbertson at WSU, have shattered this simplistic understanding. Tannins are polymers of flavon-3-ols. According to Harbertson’s work, longer tannins are usually perceived as more astringent, yet seed tannins are about a third of the length of skin tannins, averaging ten instead of thirty units. On the other hand, seed tannins take longer to extract than skin tannins; even though seed tannins outweigh skin tannins in magnitude, they release more slowly. To add yet another layer of complexity, the make-up of each tannin polymer influences its sensory characteristics in addition to its sheer length. And even then tannin experts haven’t yet deciphered what happens to tannins over time to make well-aged wine seem softer and less harsh than its youthful counterpart. For more on this topic without delving into the scientific literature, try this palatable Wines and Vines article.
The upshot of how to use délestage in the face of all of this complex chemistry? Taste, taste, taste. I’m no winemaker, but isn’t this self-evident? Superb winemakers have been making superb wine for centuries before anyone ever named or knew of a flavon-3-ol. Intuitively, it makes sense that removing seeds will reduce seed-y flavors. If that makes your wine taste better, go for it. As for oxygen, even if it remains the great unknown variable, scientific uncertainty doesn’t invalidate your taste buds.
*Cap management – grape skins are pushed, parachute-like, to the top of the must by CO2 bubbles created by the fermentation process, creating a “cap” of skins that can literally float above the surface of the must. Free from the protective effects of alcohol and acid and exposed to air, this cap will rapidly submit to spoilage microorganisms if not frequently reincorporated into the must. Hence, in making red wines, the “cap” must be “managed.”
Erika Szymanski is an independent contributor to this blog. She is in no way affiliated with the sponsoring company. This blog was originally posted on her blog: The Wine-o-scope.